Generation of the SCF3 Radical by Photoredox Catalysis: Intra- and Intermolecular Carbotrifluoromethylthiolation of Alkenes
Generation of the SCF3 Radical by Photoredox Catalysis: Intra- and Intermolecular Carbotrifluoromethylthiolation of Alkenes
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DOI：
10.1002/chem.201700734
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发表时间：
2017-03-28
影响因子：
4.3
通讯作者：
Magnier, Emmanuel
中科院分区：
文献类型：
--
作者：
Dagousset, Guillaume;Simon, Cedric;Magnier, Emmanuel
我们报道了在光氧化还原催化下，N-三氟甲基硫代异硫氰酸酯作为SCF 3自由基的来源的首次使用。这使得一个有效的和一般的cofluoromethyl光介导的烯烃硫醇化。在优化的条件下，使用fac-[Ir（ppy）（3）]作为光催化剂，各种N-芳基丙烯酰胺以及广泛的取代苯乙烯可以容易地以分子内或分子间的方式进行双官能化，以良好至优异的产率提供相应的含SCF 3的产物。重要的是，由于自旋捕获/电子顺磁共振（ST/EPR）实验，该SCF 3自由基沿着与其他关键自由基中间体的形成被明确地证明，这使得能够清楚地理解反应机理。
We report the first use of N-trifluoromethylthiosaccharin as the source of SCF3 radical under photoredox catalysis. This allowed an efficient and general visiblelight-mediated carbotrifluoromethylthiolation of alkenes. Under the optimized conditions using fac-[Ir(ppy)(3)] as the photocatalyst, various N-aryl acrylamides as well as a wide range of substituted styrenes can readily be difunctional-ized in an intra- or intermolecular fashion, affording the corresponding SCF3-containing products in good to excellent yield. Importantly, the formation of this SCF3 radical along with other key radical intermediates was unambiguously demonstrated thanks to spin trapping/electron paramagnetic resonance (ST/EPR) experiments, which enabled a clear understanding of the reaction mechanism.